Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS4465790 A
Publication typeGrant
Application numberUS 06/476,168
Publication dateAug 14, 1984
Filing dateMar 17, 1983
Priority dateMar 17, 1983
Fee statusPaid
Publication number06476168, 476168, US 4465790 A, US 4465790A, US-A-4465790, US4465790 A, US4465790A
InventorsWilliam H. Quayle
Original AssigneeAmerican Cyanamid Company
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Hydrotreating catalyst
US 4465790 A
Abstract
Improved hydrodenitrogenation catalysts comprise catalytic metals, e.g. molybdenum and nickel, on supports of co-precipitated alumina and titania with more than 5% of the catalyst weight consisting of titanium oxide in the support.
Images(3)
Previous page
Next page
Claims(2)
We claim:
1. Hydrodenitrogenation catalyst comprising catalytic molybdenum and nickel on a catalyst support consisting essentially of co-precipitated alumina and titania with an amount of titania in the support sufficient to constitute more than 5% of the catalyst weight of a finished hydrodenitrogenation catalyst made on said support.
2. Hydrodenitrogenation catalyst defined by claim 1 wherein the titania content of the catalyst support constitutes from about 6 to about 8% of the total catalyst weight.
Description

The invention relates to improvements in catalysts useful for catalytic hydrotreating of petroleum distillation fractions and residues. More particularly the invention provides improved catalysts for removal of nitrogen compounds from oils by catalytic treatment with hydrogen.

Catalytic hydrotreating processes are known for petroleum refining, using catalysts comprising metals of groups VI - A and VIII on catalyst supports of alumina or alumina-silica or the like. One such process is catalytic hydrodenitrogenation (HDN) in which the catalytic metals molybdenum and nickel on suitable supports are particularly effective in combination for removal of nitrogen compounds from oils by catalytic treatment with hydrogen.

U.S. Pat. No. 3,016,346 described nickel molybdenum catalysts on supports consisting of alumina and minor amount (0.5 to 5 wt. %) of titania. The finished catalysts contained not more than about 10% by wt of molybdenum. The utilization of small proportions of titania instead of silica in the supports described resulted in improved HDN activity and reduced hydrocracking when the supported catalysts were used for catalytic hydrotreating of middle fraction naphtha in a standard relative activity test. The alumina-titania support used in that test was prepared by a method starting with co-precipitation of aluminum and titanium hydroxides from a solution of titanium tetrachloride and aluminum chloride. A finished alumina-titania support containing 3.7 wt. % titania and about 6% molybdenum was described.

The present invention utilizes catalyst supports of alumina-titania prepared by a process starting with co-precipitation of the metals as a hydrogel from a solution of the sulfates of aluminum and titanium. The hydrogel is washed and dried and the resulting powder is mulled with acid and water to make an extrudable paste. The paste is extruded and the extrudates are dried and calcined to finish the catalyst support. The calcined support is impregnated with a solution of the catalytic metal salts, then dried and calcined again to produce the finished catalyst.

Molybdenum loadings in the range from about 10 to about 25% by wt (as MoO3) and nickel loadings from about 2 to about 10% by wt (as NiO) based on the weight of the finished catalyst are typical catalytic metal loadings for hydrodenitrogenation catalysts embodying the invention. Cobalt may also be present in amounts from about 2 to about 10% (as CoO) by wt of the finished catalyst.

We use amounts of titania in the support to constitute more than 5%, up to about 40% based on the weight of the finished catalyst. We prefer, however, to use supports made as described, to contain titania in an amount to constitute about 6 to 8% of the finished catalyst weight.

The invention is described in more detail with reference to specific examples described below.

Example 1

A solution containing alum and titanium was made from 113 lbs. Al2 (SO4)3.14H2 O, 130 lb. Ti(SO4)2.H2 SO4 solution (8.3% TiO2) and 147 lb. H2 O. A sodium aluminate solution was made from 90 lb. NaOH, 152 lb. Al2 O3 -3H2 O and 120 lb. H2 O. The alum and sodium aluminate solutions were added simultaneously to a heel of 640 lb. H2 O, 2.4 lb. 50% gluconic acid and 20 lb. alum solution. The starting temperature was 54 C. and during the addition a pH of 8.5 was maintained. Addition of excess sodium aluminate raised the pH to 10.2. The slurry was filtered and washed twice and then spray dried. One kg of spray dried powder was mulled with 0.7 kg H2 O and 22.5 ml concentrated nitric acid for 50 minutes, extruded into trilobal shaped granules, dried and calcined to give a desired pore structure. The calcined granules were impregnated in a single step with a solution containing nickel, molybdenum and phosphorus. Subsequent drying and calcining provided a catalyst containing nominally 18 wt. % MoO3, 3 wt. % NiO, 3 wt. % P, 7 wt. % TiO2 and the remainder, Al2 O3.

Example 2

Same as for Example 1 except that 155 lb. Al2 (SO4)3.14H2 O, 82 lb. Ti(SO4)2.H2 SO4 solution and 204 lb. H2 O comprised the alum solution; 145 lb. NaOH, 235 lb. Al2 O3.3H2 O and 184 lb. H2 O comprised the sodium aluminate solution; 1100 lb. H2 O, 2 lb. 50% gluconic acid and 33 lb. alum solution comprised the heel; and the addition pH was maintained at 8.0. One kg of the spray dried powder was mulled with 1 kg H2 O and 7.5 ml concentrated nitric acid. After workup and impregnation the catalyst contained nominally 18% MoO3, 3% NiO, 3% P, 4% TiO2 and the remainder Al2 O3.

Example 3

Catalysts made as described in Examples 1 and 2 were tested in a standardized laboratory test for determining hydrodenitrogenation activity for the catalysts tested.

A 1" diameter fixed-bed catalytic reactor is loaded with 100 ml hydrodenitrogenation catalyst and the catalyst is presulfided using 10% H2 S in H2 at the rate 5.5 SCFH, pressure 200 psig and temperatures increasing from 150 to about 700 F. over a period of about eight hours. The bed is then cooled to 450 F. while continuing the H2 S flow at a diminishing rate. The bed is then ready for the hydrotreating process. The reactor is operated at 1400 psig, H2 flow rate 6000 SCF/BBl. With the reactor bed at 450 F., the oil feed is started and a 5% NaOH aqueous solution is fed with the oil at the same liquid volume rate. The bed temperature is raised at a fixed rate to 725 F., at which the temperature is maintained for 60 hours operating time. Samples are taken every 6 hours and analyzed for nitrogen content. Relative HDN activity on a weight basis (RWA) and relative HDN activity on a volume basis (RVA) are calculated from results of the analysis. These activity values compare the measured HDN activity of the test catalyst with that of a conrol HDN catalyst, as measured in an identical test, on basis of activity per unit weight of the test and control catalysts, and activity per unit volume of the test and control catalyst. The activity of the control is assigned a value of 100. A relative activity value of 110 for example indicates activity 10% higher than that of the control.

The control catalyst is a commercial HDN catalyst having the same nominal catalytic metals loading as the test catalysts, on supports made of precipitated alumina.

The oil used for the tests has the specifications shown in Table 1 below.

              TABLE 1______________________________________Designation              Gas Oil______________________________________Gravity, API @ 60 F.                    23.5Nitrogen, Total, (KJEL) wt %                    0.305Nitrogen, Basic, wt %    0.138Sulfur, wt %             1.94Hydrogen, micro, wt %    11.9Carbon, micro, wt %      86.1Aniline Point, F.                    117.7Carbon Residue on 10% Botts, wt %                    0.24Fischer Water (UTM-21) mg/l                    0.36Pour Point, F.   +5Flash Point, PMCC, F.                    202Composition: Volume % (Univ. High Mass)Total Aromatics          31.4Monoaromatics            14.6Diaromatics              9.1Triaromatics             4.7Tentraromatics           1.9Pentraromatics           1.1Total Olefins            9.0Total Saturates          35.8Oxygen & Nitrogen Compounds                    5.0Sulfur Compounds         18.7______________________________________DistillationVol % - IBP  5      30       50   80    E.P.F. - 200       505    582      637  717    805______________________________________

In a series of six tests carried out as described above, testing catalyst samples made as described in Example 1, on supports having about 7 wt % titania, the RWA values were 119, 123, 127, 130, 134 and 137 respectively and the RVA values were 120, 123, 124, 124, 134 and 130, respectively.

In two tests of catalysts made as described in Example 2, containing nominal 4% titania based on total catalyst weight, the RWA values were 95 and 102 and the RVA values were 95 and 97, respectively.

Except for occasional anomalous test results, the HDN catalysts made on alumina-titania supports and which contain more than 5% by wt titania, are found to generally have higher HDN activity than those containing less than 5% of titania.

Catalysts made with catalytic metals loading equivalent to those above on co-precipitated aluminia-titania supports and containing titania in amounts about 16 and 18% by wt, respectively were tested and found to have relative activities 96 RWA, 91 RVA and 114 RWA, 119 RVA, respectively.

The use of sulfates instead of chlorides in the co-precipitation of alumina and titania results in a finished catalyst support that contains less residual chloride, and this provides the advantage that the catalyst is less corrosive than one containing more chloride, when used in steel reactor equipment.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US1822848 *Oct 21, 1929Sep 8, 1931Silica Gel CorpMethod of preparing plural gels
US2319948 *Jul 5, 1940May 25, 1943Standard Oil CoCatalytic process of treating hydrocarbons
US3016346 *May 25, 1960Jan 9, 1962Universal Oil Prod CoHydrodesulfurization process and catalyst therefor
US3262874 *Jan 29, 1964Jul 26, 1966Universal Oil Prod CoHydrorefining of petroleum crude oil and catalyst therefor
US3394077 *Nov 1, 1965Jul 23, 1968Sinclair Research IncHydrorefining in the presence of low hydrogen sulfide partial pressures
US4196101 *Feb 3, 1978Apr 1, 1980Filtrol CorporationProcess for forming alumina pellets containing titania and process for producing hydrodesulfurization catalyst containing the pellets
US4382854 *Dec 16, 1980May 10, 1983Kaiser Aluminum & Chemical CorporationNi/Co Mo P on titania-alumina hydrodesulfurizing catalyst and process of hydrodesulfurizing using the same
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4657663 *Apr 24, 1985Apr 14, 1987Phillips Petroleum CompanyHydrotreating process employing a three-stage catalyst system wherein a titanium compound is employed in the second stage
US4687757 *Mar 24, 1986Aug 18, 1987Phillips Petroleum CompanyHydrofining catalyst composition and process for its preparation
US4734186 *May 18, 1987Mar 29, 1988Phillips Petroleum CompanyHydrofining process
US5089453 *Jun 25, 1990Feb 18, 1992Chevron Research And Technology CompanyHydroconversion catalyst and method for making the catalyst
US5089462 *Jun 25, 1990Feb 18, 1992Chevron Research And Technology CompanyHydroconversion catalyst and method for making the catalyst
US5190641 *Nov 13, 1991Mar 2, 1993Chevron Research And Technology CompanyHydroconversion catalyst
US5190642 *Nov 13, 1991Mar 2, 1993Chevron Research And Technology CompanyHydroconversion catalyst
US5229347 *May 8, 1991Jul 20, 1993Intevep, S.A.Catalyst for mild hydrocracking of cracked feedstocks and method for its preparation
US5254240 *Feb 18, 1992Oct 19, 1993Intevep, S.A.Hydrocracking of petroleum feedstocks using a tri-elemental catalyst with a titania-alumina support
US5558766 *Oct 24, 1994Sep 24, 1996Intevep, S.A.Hydrocracking of feedstocks and catalyst therefor
US5962367 *May 2, 1997Oct 5, 1999Dequing Chemical Industry And Technologies Co., Ltd.Titania (TiO2) support and process for preparation and use of the same
US6019954 *Aug 14, 1996Feb 1, 2000China Petro-Chemical CorpCatalyst and process for the conversion of carbon monoxide
US6036847 *Mar 26, 1996Mar 14, 2000W. R. Grace & Co.-Conn.Compositions for use in catalytic cracking to make reduced sulfur content gasoline
US6383975 *Jul 1, 1999May 7, 2002Instituto Mexicano Del PetroleoProcedure to obtain a catalyst for the hydrodenitrogenation and hydrodesulfurization of middle and heavy oil fraction and the resulting product
US7977450Jul 12, 2011Board Of Trustees Of Michigan State UniversitySynthesis of caprolactam from lysine
US8283466Feb 20, 2008Oct 9, 2012Board Of Trustees Of Michigan State UniversityCatalytic deamination for caprolactam production
US8367819Feb 5, 2013Board Of Trustees Of Michigan State UniversitySynthesis of caprolactam from lysine
US9415384Jun 20, 2013Aug 16, 2016Advanced Refining Technologies LlcResid hydrotreating catalyst containing titania
US20090005532 *Jun 26, 2008Jan 1, 2009Board Of Trustees Of Michigan State UniversitySynthesis of caprolactam from lysine
US20100145003 *Feb 20, 2008Jun 10, 2010Board Of Trustees Of Michigan State UniversityCatalytic Deamination for Caprolactam Production
US20110190488 *Jul 24, 2009Aug 4, 2011Wicks Douglas AMethods of Making Cyclic Amide Monomers and Related Derivatives
CN1088093C *May 18, 1999Jul 24, 2002中国石油化工集团公司Process for preparing hydrorefining catalyst
CN1094072C *Apr 30, 1999Nov 13, 2002北京海顺德钛催化剂有限公司Hydrodesulphurization method of gas containing hydrocarbon, and catalyst and its application
EP0199399A2 *Apr 1, 1986Oct 29, 1986Shell Internationale Research Maatschappij B.V.Improved hydroconversion catalyst and process
EP0512835A1 *May 7, 1992Nov 11, 1992Intevep SACatalyst for mild hydrocracking of cracked feedstocks and method for its preparation
EP2864042A4 *Jun 20, 2013Apr 13, 2016Advanced Refining Technologies LlcImproved resid hydrotreating catalyst containing titania
WO1992000141A1 *Jun 6, 1991Jan 9, 1992Chevron Research And Technology CompanyHydroconversion catalyst, method of making the catalyst and method for the hydrodenitrogenation of a hydrocarbon feed using the catalyst
WO1992000142A1 *Jun 6, 1991Jan 9, 1992Chevron Research And Technology CompanyHydroconversion catalyst
WO1996014152A1 *Nov 4, 1994May 17, 1996Deqing Chemical Industry And Technology Development CompanyTITANIA (TiO2) SUPPORT AND PROCESS FOR ITS PREPARATION AND USE THE SAME
WO2013192394A1 *Jun 20, 2013Dec 27, 2013Advanced Refining Technologies LlcImproved resid hydrotreating catalyst containing titania
Classifications
U.S. Classification502/309, 208/254.00H
International ClassificationC10G35/00, C10G45/08, B01J37/03, B01J21/06, B01J23/00, B01J23/883
Cooperative ClassificationB01J23/883, C10G45/08, B01J21/063, B01J37/03
European ClassificationB01J23/883, C10G45/08
Legal Events
DateCodeEventDescription
Mar 17, 1983ASAssignment
Owner name: AMERICAN CYANAMID COMPANY, 1937 WEST MAIN ST., STA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:QUAYLE, WILLIAM H.;REEL/FRAME:004111/0217
Effective date: 19830315
Oct 26, 1987FPAYFee payment
Year of fee payment: 4
Jan 30, 1992FPAYFee payment
Year of fee payment: 8
Jan 19, 1996FPAYFee payment
Year of fee payment: 12
Mar 7, 2001ASAssignment
Owner name: SHELL OIL COMPANY, TEXAS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:CYTEC TECHNOLOGY CORP.;CYTEC INDUSTRIES;REEL/FRAME:011601/0717
Effective date: 20001222